Phthalimidylazo dyes, processess for the preparation thereof and the use thereof

ABSTRACT

The present invention relates to dyes of formula (I) wherein R 1  is C 1 –C 12 alkyl or —C n H 2n —(OCH 2 CH 2 ) m —OR 3 , n being a number from 2 to 8, m being a number from 0 to 4 and R 3  being C 1 –C 12 alkyl, C 6 –C 24 aryl or C 6 –C 24 aralkyl, R 2  is methyl, ethyl, n-propyl, n-butyl, 2-methoxyethyl or 2-ethoxyethyl, X is halogen and Y is hydrogen, chlorine or bromine, and to the process for the preparation thereof and to the use thereof in dyeing or printing semi-synthetic and especially synthetic hydrophobic fiber materials, more especially textile materials

The present invention relates to disperse dyes having anN-alkyl-phthalimide diazo component and a pyridone coupling component,to processes for the preparation of such dyes and to the use thereof indyeing or printing semi-synthetic and especially synthetic hydrophobicfibre materials, more especially textile materials.

Disperse azo dyes having an N-alkyl-phthalimide diazo component and apyridone coupling component have been known for a long time and are usedin dyeing hydrophobic fibre materials. It has, however, been found thatthe dyeings or prints obtained using the currently known dyes do not inall cases satisfy today's requirements, especially in respect offastness to washing and fastness to perspiration. There is therefore aneed for new dyes that especially have good washing fastness properties.

It has now been found, surprisingly, that the dyes according to theinvention meet the criteria given above to a considerable degree.

The present invention accordingly relates to disperse dyes that yielddyeings having a high degree of fastness to washing and to perspirationand that, in addition, have good build-up characteristics both in theexhaust and thermosol processes and in textile printing. The dyes arealso suitable for discharge printing.

The dyes according to the Invention correspond to formula

wherein R₁ is C₁–C₁₂alkyl or —C_(n)H_(2n)—(OCH₂CH₂)_(m)—OR₃, n being anumber from 2 to 8,M being a number from 0 to 4 and R₃ beingC₁–C₁₂alkyl, C₆–C₂₄aryl or C₆–C₂₄aralkyl,

-   R₂ is methyl, ethyl, n-propyl, n-butyl, 2-methoxyethyl or    2-ethoxyethyl,-   X is halogen and Y Is hydrogen, chlorine or bromine.

C₁–C₁₂Alkyl as R₁ and R₃ may be, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,neopentyl, n-hexyl, n-octyl, n-decyl or n-dodecyl.

C₆–C₂₄Aryl groups as R₃ are, for example, phenyl, tolyl, mesityl,isityl, naphthyl and anthryl.

Suitable C₆–C₂₄aralkyl groups are, for example, benzyl and2-phenylethyl.

Preference is given to dyes of formula (1) wherein R₁ is methyl, ethylor n-butyl.

R₂ is preferably n-butyl.

Halogen as X is fluorine, chlorine or, preferably, bromine.

Y is preferably hydrogen.

Special reference is given to dyes of formulae (1a), (1b) and (1c)

The present invention relates also to the process for the preparation ofthe dyes of formula (1), which comprises nitration of a phthalimide offormula

wherein R₂ is as defined hereinbefore, in the acid range, as described,for example, on page 459 in Organic Synthesis, Collective Volume 2, (aRevised Edition of Annual Volumes X–XIX), J. Wiley & Sons, followed byalkylaton of the resulting nitro compound, for example in accordancewith a method described in Journal of Organic Chemistry 32 (1967) onpage 1923, paragraph 3, and, for example after a reductive treatmentdescribed In Bull. Soc. Chim. de France 1957 on page 569, conversioninto an intermediate of formula

halogenation of the intermediate of formula (3) in an acid medium andthen diazotisation and coupling to a pyridone compound of formula (4)

wherein R₁ is as defined hereinbefore.

The halogenation is carried out, for example, by reacting the compoundof formula (3) first with sodium acetate in acetic acid and then withbromine in the same medium to form the corresponding monobromo compound.

The diazotisation is likewise carried out in a manner known per se, forexample with sodium nitrite in an acidic, for examplehydrochloric-acid-containing or sulfuric-acid-containing, aqueousmedium. The diazotisation may, however, also be carried out using otherdiazotisation agents, e.g. using nitrosylsulfuric acid. In thediazotisation, an additional acid may be present in the reaction medium,e.g. phosphoric acid, sulfuric acid, acetic acid, propionic acid,hydrochloric acid or mixtures of such acids, e.g. mixtures of propionicacid and acetic acid. The diazotisation is advantageously carried out attemperatures of from −10 to 30° C., e.g. from −10° C. to roomtemperature.

The coupling of the diazotised compound to the coupling component offormula (4) is likewise effected in known manner, for example in anacidic, aqueous or aqueous-organic medium, advantageously attemperatures of from −10 to 30° C., especially below 10° C. Examples ofacids used are hydrochloric acid, acetic acid, propionic acid, sulfuricacid and phosphoric add.

The diazo components and the coupling components of formula (4) areknown or can be prepared in a manner known per se.

The present invention relates also to dye mixtures comprising at leasttwo structurally different azo dyes of formula (1).

The dye mixtures according to the invention comprising at least twostructurally different azo dyes of formula (1) can be prepared, forexample, by simply mixing the individual dyes.

The amounts of the individual dyes in the dye mixtures according to theinvention can vary within a wide range, for example from 95:5 to 5:95parts by weight, especially from 70:30 to 30:70 parts by weight, moreespecially from 55:45 to 45:55 parts by weight, of the individual dyesin a dye mixture comprising two azo dyes according to the invention.

The dyes and dye mixtures according to the invention may be used fordyeing or printing semi-synthetic and especially synthetic hydrophobicfibre materials, more especially textile materials. Textile materialscomposed of blend fabrics that comprise such semi-synthetic or synthetichydrophobic fibre materials can also be dyed or printed using the dyesor dye mixtures according to the invention.

Semi-synthetic fibre materials that come into consideration are,especially, cellulose 2½ acetate and cellulose triacetate.

Synthetic hydrophobic fibre materials consist especially of linear,aromatic polyesters, for example those of terephthalic acid and glycols,especially ethylene glycol, or condensation products of terephthalicacid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g.those of α,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and offibres based on polyvinyl chloride or on polyamide.

The application of the dyes and dye mixtures according to the inventionto the fibre materials is effected in accordance with known dyeingmethods. For example, polyester fibre materials are dyed in the exhaustprocess from an aqueous dispersion in the presence of customary anionicor non-ionic dispersants and, optionally, customary swelling agents(carriers) at temperatures of from 80 to 140° C. Cellulose 2½ acetate isdyed preferably at from 65 to 85° C. and cellulose triacetate attemperatures of from 65 to 115° C.

The dyes and dye mixtures according to the invention will not colourwool and cotton present at the same time in the dyebath or will coloursuch materials only slightly (very good reservation) so that they canalso be used satisfactorily in the dyeing of polyester/wool andpolyester/cellulosic fibre blend fabrics.

The dyes and dye mixtures according to the invention are suitable fordyeing in accordance with the thermosol process, in the exhaust processand for printing processes.

In such processes, the said fibre materials can be in a variety ofprocessing forms, e.g. in the form of fibres, yarns or nonwoven, wovenor knitted fabrics.

It is advantageous to convert the dyes or dye mixtures according to theinvention into a dye preparation prior to use. For this purpose, the dyeis ground so that its particle size is on average from 0.1 to 10microns. Grinding can be carried out in the presence of dispersants. Forexample, the dried dye is ground together with a dispersant or kneadedinto a paste form together with a dispersant and then dried in vacuo orby atomisation. After adding water, the resulting preparations can beused to prepare printing pastes and dyebaths.

For printing, the customary thickeners will be used, e.g. modified orunmodified natural products, for example alginates, British gum, gumarabic, crystal gum, locust bean flour, tragacanth, carboxymethylcellulose, hydroxyethyl cellulose, starch or synthetic products, forexample polyacrylamides, polyacrylic acid or copolymers thereof, orpolyvinyl alcohols.

The dyes and dye mixtures according to the invention impart to the saidmaterials, especially to polyester materials, level colour shades havingvery good in-use fastness properties such as, especially, good fastnessto light, fastness to heat setting, fastness to pleating, fastness tochlorine, and wet fastness, e.g. fastness to water, to perspiration andto washing; the finished dyeings are further characterised by very goodfastness to rubbing. Special emphasis should be given to the goodfastness properties of the dyeings obtained with respect to perspirationand, especially, to washing.

The dyes and dye mixtures according to the invention can also be usedsatisfactorily in producing mixed shades together with other dyes.

Furthermore, the dyes and dye mixtures according to the invention arealso well suited to dyeing hydrophobic fibre materials fromsupercritical CO₂.

The present invention relates to the above-mentioned use of the dyes anddye mixtures according to the invention as well as to a process for thedyeing or printing of semi-synthetic or synthetic hydrophobic fibrematerials, especially textile materials, in which process a dyeaccording to the invention is applied to the said materials orincorporated into them. The said hydrophobic fibre materials arepreferably textile polyester materials. Further substrates that can betreated by the process according to the invention and preferred processconditions can be found hereinbefore in the more detailed description ofthe use of the dyes according to the invention.

The invention relates also to hydrophobic fibre materials, preferablypolyester textile materials, dyed or printed by the said process.

The dyes according to the invention are, in addition, suitable for modemreproduction processes, e.g. thermotransfer printing.

The Examples that follow serve to illustrate the invention. Partstherein are parts by weight and percentages are percentages by weight,unless otherwise indicated. Temperatures are given in degrees Celsius.The relationship between parts by weight and parts by volume is the sameas between grams and cubic centimetres.

I. PREPARATION EXAMPLES Example I.1

A. Diazotisation

5 ml of 96% sulfuric acid are transferred to a laboratory reactionapparatus. With stirring, 2.7 ml of ice-water are slowly added dropwiseso that the internal temperature is 25–30° C. Then, over the course of20 minutes, 3.0 g of 4-amino-5-bromo-N-butylphthalimide are introduced.The resulting suspension is stirred for 10 minutes at an internaltemperature of 25–30° C. Then, over the course of 15 minutes, 1.75 ml of40% nitrosylsulfuric acid are added dropwise at an internal temperatureof 20–25° C. and stirred for 2 hours at that temperature.

B. Coupling

A solution of 3 drops of Surfynol 104 E(2,4,7,9-tetramethyl-5-decyne-4,7-diol) in 150 ml of water istransferred to a laboratory reaction apparatus having a pH meter. Withstirring, 1.8 g of 1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone areIntroduced. Then 3 ml of 10% NaOH are added (pH=10–12). The resultingsolution is cooled to 10° C., and the solution of the diazonium salt isadded dropwise over the course of about 30 minutes so that the internaltemperature is 10–15° C., the pH being maintained at 2–3 by dropwiseaddition of 70 ml of 10% NaOH. The resulting yellow suspension isstirred for 1 hour at 10–15° C. The solid is filtered off under suction,washed with deionised water and dried. 4.7 g (86% of Theory) of theCompound of Formula

are obtained.

-   Melting point: >150° C.-   Appearance: yellow-green

Analogously to Example I.1, the following dyes can be prepared, whichare likewise suitable for dyeing semi-synthetic or synthetic hydrophobicfibre materials (Table 1):

TABLE 1

X Y R₁ R₂ Br H CH₃ CH₃ Br H CH₃ C₂H₅ Br H CH₃ n-C₃H₇ Br H CH₃ n-C₄H₉ BrH CH₃ —CH₂CH₂OCH₃ Br H CH₃ —CH₂CH₂OC₂H₅ Br H C₂H₅ CH₃ Br H C₂H₅ C₂H₅ BrH C₂H₅ n-C₃H₇ Br H C₂H₅ n-C₄H₉ Br H C₂H₅ —CH₂CH₂OCH₃ Br H C₂H₅—CH₂CH₂OC₂H₅ Br H n-C₃H₇ CH₃ Br H n-C₃H₇ C₂H₅ Br H n-C₃H₇ n-C₃H₇ Br Hn-C₃H₇ n-C₄H₉ Br H n-C₃H₇ —CH₂CH₂OCH₃ Br H n-C₃H₇ —CH₂CH₂OC₂H₅ Br Hn-C₄H₉ CH₃ Br H n-C₄H₉ C₂H₅ Br H n-C₄H₉ n-C₃H₇ Br H n-C₄H₉ n-C₄H₉ Br Hn-C₄H₉ —CH₂CH₂OCH₃ Br H n-C₄H₉ —CH₂CH₂OC₂H₅ Br H —CH₂CH₂OCH₃ CH₃ Br H—CH₂CH₂OCH₃ C₂H₅ Br H —CH₂CH₂OCH₃ n-C₃H₇ Br H —CH₂CH₂OCH₃ n-C₄H₉ Br H—CH₂CH₂OCH₃ —CH₂CH₂OCH₃ Br H —CH₂CH₂OCH₃ —CH₂CH₂OC₂H₅ Br H—CH₂CH₂CH₂OCH₂CH₂OCH₃ CH₃ Br H —CH₂CH₂CH₂OCH₂CH₂OCH₃ C₂H₅ Br H—CH₂CH₂CH₂OCH₂CH₂OCH₃ n-C₃H₇ Br H —CH₂CH₂CH₂OCH₂CH₂OCH₃ n-C₄H₉ Br H—CH₂CH₂CH₂OCH₂CH₂OCH₃ —CH₂CH₂OCH₃ Br H —CH₂CH₂CH₂OCH₂CH₂OCH₃—CH₂CH₂OC₂H₅ Br H

CH₃ Br H

C₂H₅ Br H

n-C₃H₇ Br H

n-C₄H₉ Br H

—CH₂CH₂OCH₃ Br H

—CH₂CH₂OC₂H₅ Br Br CH₃ CH₃ Br Br CH₃ C₂H₅ Br Br CH₃ n-C₃H₇ Br Br CH₃n-C₄H₉ Br Br CH₃ —CH₂CH₂OCH₃ Br Br CH₃ —CH₂CH₂OC₂H₅ Br Br C₂H₅ CH₃ Br BrC₂H₅ C₂H₅ Br Br C₂H₅ n-C₃H₇ Br Br C₂H₅ n-C₄H₉ Br Br C₂H₅ —CH₂CH₂OCH₃ BrBr C₂H₅ —CH₂CH₂OC₂H₅ Br Br n-C₃H₇ CH₃ Br Br n-C₃H₇ C₂H₅ Br Br n-C₃H₇n-C₃H₇ Br Br n-C₃H₇ n-C₄H₉ Br Br n-C₃H₇ —CH₂CH₂OCH₃ Br Br n-C₃H₇—CH₂CH₂OC₂H₅ Br Br n-C₄H₉ CH₃ Br Br n-C₄H₉ C₂H₅ Br Br n-C₄H₉ n-C₃H₇ BrBr n-C₄H₉ n-C₄H₉ Br Br n-C₄H₉ —CH₂CH₂OCH₃ Br Br n-C₄H₉ —CH₂CH₂OC₂H₅ BrBr —CH₂CH₂OCH₃ CH₃ Br Br —CH₂CH₂OCH₃ C₂H₅ Br Br —CH₂CH₂OCH₃ n-C₃H₇ Br Br—CH₂CH₂OCH₃ n-C₄H₉ Br Br —CH₂CH₂OCH₃ —CH₂CH₂OCH₃ Br Br —CH₂CH₂OCH₃—CH₂CH₂OC₂H₅ Br Br —CH₂CH₂CH₂OCH₂CH₂OCH₃ CH₃ Br Br —CH₂CH₂CH₂OCH₂CH₂OCH₃C₂H₅ Br Br —CH₂CH₂CH₂OCH₂CH₂OCH₃ n-C₃H₇ Br Br —CH₂CH₂CH₂OCH₂CH₂OCH₃n-C₄H₉ Br Br —CH₂CH₂CH₂OCH₂CH₂OCH₃ —CH₂CH₂OCH₃ Br Br—CH₂CH₂CH₂OCH₂CH₂OCH₃ —CH₂CH₂OC₂H₅ Br Br

CH₃ Br Br

C₂H₅ Br Br

n-C₃H₇ Br Br

n-C₄H₉ Br Br

—CH₂CH₂OCH₃ Br Br

—CH₂CH₂OC₂H₅

II. APPLICATION EXAMPLES Example II.1

1 Part by Weight of the Dye of Formula

is ground in a sand mill, together with 17 parts by weight of water and2 parts by weight of a commercially available dispersant of thedinaphthylmethane disulfonate type, and converted into a 5% aqueousdispersion.

Using that formulation, a 1% dyeing (based on the dye and the substrate)is produced on woven polyester fabric by the high-temperature exhaustprocess at 130° C. and is cleared reductively. The violet dyeingobtained in that manner has very good in-use fastness properties,especially excellent fastness to washing.

The same good fastness properties can be achieved when woven polyesterfabric is dyed in the thermosol process (10 g/liter of dye, liquorpick-up 50%, fixing temperature 210° C.).

1. A dye of formula

wherein R₁ is C₁–C₁₂alkyl or —C_(n)H_(2n)—(OCH₂CH₂)_(m)—OR₃, n being anumber from 2 to 8, m being a number from 0 to 4 and R₃ beingC₁–C₁₂alkyl, C₆–C₂₄aryl or C₆–C₂₄aralkyl, R₂ is n-butyl, X is halogenand Y is hydrogen, chlorine or bromine.
 2. A dye of formula (1)according to claim 1, wherein R₁ is methyl, ethyl or n-butyl.
 3. A dyeof formula (1) according to claim 1, wherein X is bromine.
 4. A dye offormula (1) according to claim 1, wherein Y is hydrogen.
 5. A dye offormula (1a), (1b) or (1c)


6. A process for the preparation of a dye of formula (1d),

wherein R₁ is C₁–C₁₂alkyl or —C_(n)H_(2n)—(OCH₂CH₂)_(m)—OR₃, n being anumber from 2 to 8, m being a number from 0 to 4 and R₃ beingC₁–C₁₂alkyl, C₆–C₂₄aryl or C₆–C₂₄aralkyl, R₂ is methyl, ethyl, n-propyl,n-butyl, 2-methoxyethvl or 2-ethoxyethyl, X is halogen and Y ishydrogen, chlorine or bromine which comprises nitration of a phthalimideof formula

in the acid range, followed by alkylation of the resulting nitrocompound and, by means of a reductive treatment, conversion into anintermediate of formula

halogenation of the intermediate of formula (3) in an acid medium andthen diazotisation and coupling to a pyridone compound of formula (4)


7. A dye mixture comprising at least two structurally different dyes offormula (1) according to claim
 1. 8. A process for dyeing or printingsemi-synthetic or synthetic hydrophobic fibre materials, in whichprocess a dye of formula (1) according to claim 1 is applied to the saidmaterials or incorporated into them.
 9. A semi-synthetic or synthetichydrophobic fibre material dyed or printed by the process according toclaim
 8. 10. A method of dyeing or printing semi-synthetic or synthetichydrophobic fibre materials, which comprises contacting said fibermaterials with at least one dye of formula (1) according to claim 1.